!
!
This%is%the%peer*reviewed%version%of%the%following%article: !
!
!
D.!A.!Obenchain,!L.!Sp ada,!S.!Alessandrini,!et!al.!Unveiling!the!Sulfur–Sulfur!Bridge: !
Accurate! Structural! and! Energetic! Characterization! of! a! Homochalcogen!
Intermolecular!Bond.!Angew.'Chem.''Int.'Ed.!57,!2018,!13822–13826.!!
!
Which'has'been'published'in'f inal'form'at:%
https://doi.org/10.1002/anie.201810637!
This'article'may'be'used'for'non=commercial'purposes'in'accordance'with'Wiley'(o '
Wiley=VCH)'Terms'and'Conditions'for'Self=Archiving.!
!
©!2018!WileyQVCH!Verlag!Gm bH!&!Co.!KGaA, !Weinheim!
!
COMMUNICATION
1
On#the#way#to#the#sulfur0sulfur#bridge:#accurate#structural#and#
energetic#characterization#of#a#homo#chalc ogen#inter0molecular#
bond##
!"#$%&'()'*+%#,-"$#.
/"0.1
'234%#53'67"8".
/+.,0.1
'6$&9$"'(&%::"#84$#$.
/,0
'6%4;$3'<"=7$ #3.
/,0
'69%#'>%4+%4:.
/"0
'
?$,3&"'@":$#"A3.
/,0
'B"4,3'B%#83&$,,-$3.
/,0
'C%A%4'D4"E:.
/"0
'FG4;%#'H"E::.
/80
'I4$:A$#"'CE55"4$#$.
/+0
'F%#:J
KL%'H4"+3L.
/"0.
M'N$#,%#53'O"43#%
/,0.
M'
Abstract: # OP' ,3=+$#$#;' 43A"A$3#"&' :7%,A43:,37P' $#' :E7%4:3#$,'
%Q7"#:$3#' L$A-' A-% ' ,"7"+$&$AP' 3R' :A"A%J3RJA-%J"4A' SE"#AE=J,-%=$,"&'
,3=7EA"A$3#:' $#' ",,E4"A%&P' 8%A%4=$#$#;' :A4E,AE4"&' "#8' %#%4;%A$,'
7437%4A$%:.' A-%' ;%#E$#%' #"AE4%' 3R' "' :E&R E4J:E&RE4' , -"&,3; %#' +3#8'
+%AL%%#'8$=%A-P&':E&R$8%'"#8':E&RE4'8$3Q$8%'-":' +%%#' E#9%$&%8' $#'" '
;":JT%A' %#9$43#=%#A' R4%%' R43=' ,3&&$:$3#.' :3&9%#A' "#8' ="A4$Q'
7%4AE4+"A$3#:)' (' 6(C@' "#"&P:$:' 73$#A%8' 3EA' A-"A' %&%,A43:A"A$,' 6!!!6'
$#A%4",A$3#:'7&"P'A-%'83=$#"#A'43&%'$#'8%A%4=$#$#;'A-%':A"+$&$AP'3R'A-%'
,3=7&%Q.'&"4;%&P'39%4,3=$#;'8$:7%4:$3#'"#8'IJ>!!!*'-P84 3;%#J+3#8'
,3#A4$+EA$3#:)' U#8%%8.' $#' ";4%%=%#A' L$A-' A-%' "#"&P:$:' 3R' A-% '
SE"84E73&%J,3E7&$ #;' ,3#:A"#A:' "#8' 3R' A-%' =%A-P&' $#A%4#"&' 4 3A"A$3#'
+"44$%4.'A-%'?O*'"#8'?* INVI!'"7743",-%:':-3L'"'="4W%8',-"4;%'
A4"#:R%4'+%AL%%#'A-%':E &RE4'"A3=:)'O":%8'3#'A-%' "::$;#=%#A'3R'A-%'
43A"A$3#"&':7%,A4"'R34'X'$:3A373&3;E%:.'"#'",,E4"A%' :%=$J%Q7%4$=%#A"&'
%SE$&$+4$E=':A4E,AE4%' R34'A-%' -%"9PJ"A3=' +",W+3#%' 3R' A-%'=3&%,E&"4 '
,3=7&%Q' -":' +%%#' 8%A%4=$#%8.' L-$,-' $:' ,-"4",A%4$5%8' +P' "' 6YYY6'
8$:A"#,%'Z[)\]XZ^_'`_'L%&&'+%&3L'A-%':E='3R'9"#'8%4'a""&:'4"8$$)'
(=3#;',-%=$,"&'%&%=%#A:.':E&RE4'$:'L$8%:74%"8'$#'#"AE4%.'"#8'$#'
7"4A$,E&"4' $#' +$3&3;$,"&&P' ",A$9%' #"AE4"&' 7438E,A:.
/b0
' L-%4%' $A'
:A43#;&P' "RR%,A:' =3&%,E&"4' 4%,3;#$A$3#' =%,-"#$:=:)
/b.[0
' (:' "'
,3#:%SE%#,%.' A-%' %RR%,A' 3R' :E+:A$AEA$3#' 3R' 3QP;%#' +P' :E&RE4' 3#'
="#P'7437%4A$%:'$:'3R'7"4A$,E&"4'4% &%9"#,%'$#'+$3,-%=$:A4P
/^0
'"#8'
,-%=$,"&' 4%",A$9$AP)
/]0
'@-%4%R34%.'A-%' $#9%:A$;"A$3#'3R'A-%',-"#;%:'
3,,E44$#;' $#' :A4E,AE4"&.
/c0
' ,-%=$,"&J7-P:$,"&
/d0
' "#8' :7%,A43:,37$,'
7437%4A$%:
/X0
'E73#':E,-':E+:A$AEA$3#'$:'3R'=E,-';%#%4"&'$#A%4%:A)'
U#' 7"4"&&%&.' #3#J,39"&%#A' ,-"&,3;%#J+3#8' $#A%4",A$3#:' -"9%'
"AA4",A%8' =E,-' "AA%#A$3#' +%,"E:%' 3R' A-%' RE#8"=%#A"&' 43&%'A-%P'
7&"P' $#' 8$RR%4%#A' R$%&8:' :E,-' ":' ,"A"&P:$:.
/e0
' 84E;' 8%:$;#.
/b0
' :%&RJ
"::%=+&P'743,%::%:.
/\0'
"#8',4P:A"&'7",W$#;)
/bf0
'K#8%4:A"#8$#;'A-%'
=%,-"#$:=:' "A' A-%' +":$:' 3R' A-%:%' A%,-#3&3;$,"&' 743,%::%:'
4%SE$4%:' A-%' ,-"4",A%4$5"A$3#'3R' A-%' 8$4%,A$3#"&$AP.' :A4%#;A-.' "#8'
#"AE4%' 3R' :E,-' $#A%4",A$3#:
/bb0
' ' ":' L%&&' ":' "' ,3=74%-%#:$9%'
"#"&P:$:'3R'A-%$4',3=7%A$A$3#'L$A-'3A-%4'#3#J,39"&%#A'+3#8:.' " &:3'
A"W$#;' $#A3' ",,3E#A' A-% ' AE#$#;' 3R' A-%:%' 7437%4A$%:' +P' 8$RR%4%#A'
%#9$43#=%#A:)
'
U#'A-$:'4%:7%,A.'$#'"#"&3;P'A3'A-%'-"&3;%#'+3#8
/b[0'
A-%':E&RE4'"A3=',"#'",A'%$A-%4'":'"',-"&,3;%#'+3#8'83#34'Z8E%'A3'
"' !J
/b^.b]0
'34'"J-3&%
/b^.bc0'
3#':E&RE4_'34'":'" ,,%7A34'Z+%,"E:%' 3R'"'
&3#%J7"$4'3#':E&RE4.'":'$#'A-$3%A-%4:
/b]0
_)''
@3':E=="4$5%.'A-%'9"4$%AP'3R' :E&RE4',3=73E#8:'R3E#8'$#'#"AE4%'":'
L%&&'":'A-%'8E"&'43&%'A-"A':E&RE4',"#'7&"P.',"&&'R34'"',3=74%-%#:$9%'
"#"&P:$:' "#8' ,-"4",A%4$5"A$3#' 3R' A-%' :E&RE4ggg:E&RE4' #3#,39"&%#A'
,-"&,3;%#'$#A%4",A$3#:)'(':A%7'R34L"48'$#'A-$:'8$4%,A$3#'4%SE$4%:.'
$#' "88$A$3#'A3' A-%' %&E,$8"A$3#' 3R' A-%',3#A4$+EA$3#:':A"+$&$5$#;' A-%'
$#A%4",A$3#.'A-% '",,E4"A%'W # 3 L&%8;%'3R' A- % ':A4E,AE4"&'7 " 4"=%A%4:'
$#93&9%8' $#' :E,-' &$#W";%)' !$=%A-P&' :E&R$8%' Z!B6_' $:' "' ;3 38'
,"#8$8"A%'+%,"E:%'A-%'&",W'3R' 6>' +3#8:'"93$8:' "#P',3=7%A$A$3#'
+%AL%%#' 7EA"A$9%' ,-"&,3;%#' "#8' -P843;%#' +3#8:' #%"4+P' A-%'
:"=%':E&RE4'"A3=)'(A'A-%':"=%'A$=%.'A-%'#%;"A$9%&P',-"4;%8':E&RE4'
"A3='3R'!B6':-3E&8'&%"8'A3'"' :A"+$&$5$#;'%&%,A43:A"A$,'$#A%4",A$3#'
L$A-'A-%':A43#;&P'73:$A$9%':E&RE4'"A3='3R':E&RE4' 8$3Q$8%'Z6*
[
_)'@-%'
!B6J6*
[
',3=7&%Q'-":'A- E:'+%%#':AE8$%8'+P',3=+$#$#;'43A"A$3#"&'
:7%,A43:,37P'$#':E7%4:3#$,'%Q7"#:$3#'"#8':A"A%J3RJ"4A'SE"#AE=J
,-%=$,"&' ZhI_' ,"&,E&"A$3#:.' A-E:' 4%&P$#;' 3#' A-%$4' ,"7"+$&$AP' A3'
E#9%$&' A-%' ;%#E$#%' #"AE4%' 3R' #3#J,39"&%#A' $#A%4",A$3#:' $#' "#'
%#9$43#=%#A' R4%%' R43=' :3&9"A$3#.' ="A4$Q' "#8' ,4P:A"&J7",W$#;'
%RR%,A:)'
(:'"':A"4A$#;'73$#A.'"'RE&&';%3=%A4P'37A$=$5"A$3#'L":'7%4R34=%8'+P'
=%"#:'3R'A-%':3J,"&&%8'i,-%"7j',3=73:$A%':,-%=%'8%R$#%8'$#'4%R)'
/bd0.'$#'L-$,-'A-%'II6!Z@_V,,J7N@k
/bX.be0
';%3=%A4$,"&'7"4"=%A%4:'
"4%'$=7439%8'+P'=%"#:'3R'"#'%QA4"73&"A$3#'A3'A-%',3=7&%A%'+":$:'
:%A' ZIO6_' ' &$=$A' "#8' +P' A-%' $#,&E:$3#' 3R' A- %' ,34%J9"&%#,%' ZIN_'
,3#A4$+ EA$3#.' +3A-'"A'A-%'BC['&%9%&)
/b\0
' @-$:' 37A$=$5%8' ;%3=%A4P'
Z-%4%"RA%4'4%R%44%8' A3' ":' i,-%"7j_':A4"$;-AR34L"48&P'7439$8%8' A-%'
%SE$&$+4$E='43A"A$3#"&',3#:A"#A:'Z#
%
_.'L-$,-' L%4%'A-%#',344%,A%8'
R34' 9$+4"A$3#"&' %RR%,A:
/[f0
' 3+A"$#%8' "A' A-%' O[C2lCJ!^V="E;J,,J
7N@kJ$>'&%9%&
/[b.[[0
'$#'348%4'A3'3+A"$#'A-%'9$+4"A$3#"&';43E#8J:A"A%'
43A"A$3#"&',3#:A"#A:'Z#
f
.':%%'@"+&%'b _)'@-%'O[C2lCJ!^V="E;J,,J
7N@kJ$>' ,E+$,' "#8' :%=$J8$";3#"&' SE"4A$,' ,3#:A"#A:' L%4%'"&:3'
E:%8'A3' 8%4$9%'A-%',%#A4$RE;" &J8$:A34A$3#'7"4"=%A%4:'+P'=%"#:'3R''
a"A:3#' %J4%8E,%8' >"=$&A3#$"#
/[^0
' $#' A-%' R4"=%L34W' 3R' :% ,3#8J
348%4'9$+4"A$3#"&'7%4AE4+"A$3#'A-%34P'ZNC@[_)
/[]0
'('RE&&'",,3E#A'3R'
A-%',3 =7EA"A$3#"&'8%A"$&:' A3;%A-%4'L$A-' A-%',344%:73#8$#;'4%:E&A:'
$:';$9%#'$#'A-%'6E7734A$#;'U#R34="A$3#'Z6U_)''
HE$8%8' +P' SE"#AE=J,-%=$,"&' ,"&,E&"A$3#:.' A-%' 43A"A$3#"&'
:7%,A4E=' 3R'A-%'="$#'$:3A37$,':7%,$%:'3R' A-%' !B6J6*
[
',3=7&%Q'
L":' 4%,348%8.' ":' 8%A"$&%8' $#' A-%' &'()*+,)-./01 %)2.+3-.' "#8'
"::$;#%8)' @-%' ,3=+$#"A$3#' 3R' %Q7%4$=%#A"&' 8"A"' R34' A-%' =3:A'
/"0' !4)'!)'()'*+%#,-"$#.'B4)'6.'>%4+%4:.'!4)'C)'D4"E:.'C43R)'!4)'F)K)'
H4"+3L'
U#:A$AEA'RG4'C-P:$W"&$:,-%'I-%=$%'E#8'm&%WA43,-%=$%.'
2%$+#$5'K#$9%4:$AnA'>"##39%4.'
I"&&$#:A4"o%'^(.'^fbdX'>"##39%4.'H%4="#P'
mJ="$&p'T%#:JEL%);4"+3Lq7,$)E#$J-"##39%4)8%''
/+0' !4)'2)'67"8".'C43R)'!4)'I)'CE55"4$#$'
!$7"4A$=%#A3'8$'I-$=$,"'iH$",3=3'I$"=$,$"#.j'
jK#$9%4:$Ar'8$'O3&3;#".'
N$"'6%&=$'[.'UJ]fb[d.'O3&3;#".'UA"&P'
/,0' !4)'2)'67"8".'B:)'6)'(&%::"#84$#$.'!4)'6)'<"=7$#3.'!4)'?)'@":$#"A3.'
B4)'B)'B%#83&$,,-$3.'C43R)'!4)'N)'O"43#%'
6,E3&"'?34="&%'6E7%4$34%'
C$"55"'8%$'I"9"&$%4$'X.'UJcdb[d.'C$:".'UA"&P'
mJ="$&p'9$#,%#53)+"43 #%q:#:)$A''
/80' C43R)'!4)'F)'H"E::'
U#:A$AEA'RG4'C-P:$W"&$:,-%'I-%=$%.'
F3-"##%:'HEA%#+%4;JK#$9%4:$AnA'B"$#5.'
''''''''' !E%:+%4;L%;'bfJb].'ccb[e'B"$#5.'H%4="#P '
/10' @-%:%'"EA-34:'%SE"&&P',3#A4$+EA%8'A3'A-$:'L34W)'
'
' 6E7734A$#;'$#R34="A$3#'R34'A-$:'"4A$,&%'$:';$9%#'9$"'"'&$#W'"A'A-%'%#8'3R'
A-%'83,E=%#A)'
COMMUNICATION
2
"+E#8"#A' $:3A373&3;E%' :7%,$%:' "#8' A-%' ",,E4"A%' SE"#AE=J
,-%=$,"&174%8$,A$3#:'&%8'A3'=$#$="&'"=3E#A:' 3R':%"4,-$#;'3#'A-%'
#"443LJ+"#8L$8A-' :7%,A43=%A%4.' "#8' A3' A-%' 8%A%,A$3#' 3R' X'
$:3A373&3;E%:'Z$)%).'A-%'7"4%#A':7%,$%:.'"#8'A-%':$#;&P':E+:A$AEA%8'
^]
6.'
^^
6.'
b^
I.'
be
*'$:3 A373&3;E%:_'$#'#"AE4"&'"+E#8"#,%)'s$A:'3R'A-% '
3+:%49%8' A4"#:$A$3#:' Z8%A"$&%8' &$:A:.' R34' %",-' $:3A373&3;E%.' "4%'
;$9%#' $#' @"+&%:' 6bJ6X' 3R' A-%' 6U_' L%4%' ,"44$%8' 3EA' E:$#;' A-%'
tU(B
/[c0
' 743;4"=' L$A-$#' A-%' 4
4
' 4%74%:%#A"A$3#' 3R' a"A:3#u:' %'
4%8E,A$3#)'@-%'tU(B'743;4"='L":',-3:%#' R34'$A:' ,"7"+$&$AP'A3'R$A'
A-%'=%A-P&'$#A%4#"&'43A"A$3#',3E7&$#;'"#8.'$R'"'SE"84E73&"4'#E,&%E:'
$:'74%:%#A'Z":'$#'A-%', " :%'3R':$#;&%'
^^
6J:E+:A$AEA%8':7%,$%:_.'A-%'
#E,&%"4'-P7%4R$#%':7&$AA$#;'Z" #'%Q"=7&%'$:':- 3L#'$#'s$;E4%'b'R34'
A-%'
^^
6*
[
ggg!B6':7% ,$%:_)'@-$:'"4$:%:'R43='A-%'$#A%4",A$3#'3R'A-%'
#3#J:7-%4$,"&' #E,&%"4' ,-"4;%' 8$:A4$+EA$3#' Z
^^
6' #E,&%"4' :7$#.' 41 v'
^V[_'L$A-'"'#3#5%43'%&%,A4$,'R$%&8';4"8$%#A'"A'A-%'#E,&%E:.'"#8'A-%'
,344%:73#8$#;' -P7%4R$#%' ,3=73#%#A:' "4%' &"+%&%8' E:$#;' A-%'
SE"#AE='#E=+%4'4%:E&A$#;'R43='A-%'5v4w6',3E7&$#;':,-%=%)'
'
Figure#1.'I3=+$#"A$3#'3R':%9%4"&':7%,A4"',3&&%,A%8'3#'A-%'I*O<('$#:A4E=%#A'
R34'A-%'
"
#$
% &
#'
'A4"#:$A$3#'3R'A-%'
^^
6*
[
ggg!B6'$:3A373&3;E%)'m",-'A4"#:$A$3#'$:'
:7&$A' $#A3'"' !377&%4' 7"$4' "4$:$#;' R43=' A-%',3"Q$"&'"44"#;%=%#A' 3R' A-%' T%A' "#8'
4%:3#"A34)' @-%' A-4%%' ,&3:%&P' :7",%8' A4"#:$A$3#:' "4% ' A-%' $#A%4#"&' 4 3A"A$3#'
,3=73#%#A:'&"+%&&%8'$#'A-%'&3L%:A'R4%SE%#,P':%A'Z6%%'4%R)'/[d0'R34'&"+%&:_)'m",-'
3R'A-%'R3E4':%A:'4%74%:%#A:'"'8$ RR%4%#A'5xJ5y',3=73#%#A'3R'A-%'#E,&%"4'SE"84E73&%'
-P7%4R$#%'7"AA%4#)''
a-$&%' "' RE&&' ",,3E#A' 3R' A-%' :7%,A43:,37$,' 7"4"=%A%4:' 4%:E&A$#;'
R43='A-%'R$A:'$:'7439$8%8'$#'A-%'6U.'@"+&%'b',3&&%,A:'A-%',3=7EA%8'
Z3#&P' R34' A-%' ="$#' $:3A373&3;E%_' "#8' % Q7%4$=%#A"&' 43A"A$3#"&'
,3#:A"#A:)' @-%' ,3=7"4$:3#' +%AL%%#' A-%' ,"&,E&"A%8' "#8'
%Q7%4$=%#A"&&P' 8%4$9%8' 43A"A$3#"&' ,3#:A"#A:' 73$#A:' 3EA' "' ;338'
";4%%=%#A'L$A-'8%9$"A$3#:'L%&&'L$A-$#'f)cz.'A-E:'8%=3#:A4"A$#;'
A-%'$=73 4A" #A'43 &%'7&"P%8'+P'",,E4"A%'hI',3=7EA"A$3#:'$#';E$8$#;'
A-%'4%,348$#;'"#8'"#"&P:$:'3R'A-%'43A"A$3#"&':7%,A4E=)''
Table#1.'<3A"A $3#"&',3#:A"#A:
[a]
'3R'A-%'6*
['
ggg6ZI>
^
_
[
'$:3A373&3;E%:)'
''
7'ZB>5_'
#'ZB>5_'
8'ZB>5_'
6*
['
ggg6ZI>
^
_
[
'
^]Xe)]f
/+0
'
bcf])\f
/+0
'
b[b\)X\
/+0
'
^]\f)b\[fZbd_
'
'
b]\X)Xd^eXZ]]_'
b[bd)^\d\cZ^c_'
^]
6*
['
ggg6ZI>
^
_
[
'
^]e])f[ccZ]b_'
b]XX)Xfc^]Z[e_'
b[f^)ecbb^Z[f_'
6*
['
ggg
^]
6ZI>
^
_
[
'
^]X^)\\b[Z^\_'
b]Xc)d]fd\Z[X_'
b[f^)XfbbXZb\_'
6*
['
ggg
^^
6ZI>
^
_
[
'
^]eb)\^efZ\f_'
b]ed)cbefXZ]X_'
b[f\)\d^cdZ[d_'
^^
6*
['
ggg6ZI>
^
_
[
'
^]eX)f[eZbf_'
b]eX)cX][dZ^b_'
b[bf)f^d^^Z[f_'
6
be
*
bd
*
'
ggg6ZI>
^
_
[
'
^]b])\\]eZeb_'
b]Xc)\e]^^Z[X_'
bb\])]Xc][Z[X_'
6*
[
ggg6Z
b^
I>
^
_Z
b[
I>
^
_'
^]^e)ecc\Zcd_'
b]e])XXefbZ[f_'
b[f^)^^\[eZ[f_'
/"0' ?E=+%4:' $#' 7"4%#A-%:$:' "4%' b!' E#,%4A"$#A$%:' $#' A-%' &%":A'
:$;#$R$,"#A'8$;$A)'/+0'N"&E%:'3+A"$#%8'R43='A-%34P'Z:%%'A%QA_)''
6$=$&"4&P.' ,3=7EA%8' :7%,A43:,37$,',3#:A"#A:' L%4%' 3+A"$#%8' R34'
A-%'3A-%4'$:3A37$,':7%, $%:'$# 9 % :A$;"A%8.'"&: 3 '$#,&E8$#;.'R34'A-%'
^^
6J
,3#A"$#$#;' $:3A373&3;E%:.' A-%' #E, &%"4' SE"84E73&%' ,3E7&$#;'
,3#:A"#A:)'@-%',344%:73#8$#;'4%:E&A:'"4%'R3E#8'$#'A-%'6U)'
'
I3=7EA"A$3#:' L%4%' "&:3' %QA%#8%8' A3' A-%' %9"&E"A$3#' 3R' A-%'
$#A%4",A$3#' %&%,A43#$,' %#%4;P.' A-%4%' %=7&3P$#;' "' ,3=73:$A%'
:,-%=%'"#"&3;3E:'A3'A-"A'E:%8'R34'A-%':A4E,AE4"&'%9"&E"A$3#.'L$A-'
A-%'3#&P'8$RR%4%#,%'$#'A-% '%QA4"73&"A$3#'A3'A-%'IO6'&$=$A.'L-$,-'L":'
%:A$="A%8'+P'"'AL3J:A%7'743,%8E4%.'L$A-'A-%'>sJ6Is'"#8'BC['
,344%&"A$3#' % #%4;$%:' %QA4"73 &"A%8' E:$#;' 8$RR%4%#A' R34=E&"%
/[X.[e0
)'
@-%'A3A"&'%&%,A43#$,'%#%4;P'L":'A-%#',344%,A%8'R34'A-%'5%43J73$#A'
%#%4;P'ZkCm_',3#A4$+EA$3#'3+A"$#%8'"A'A-%'O[C2lCJ!^V=J"E;J,,J
7N@kJ$>' "#-"4=3#$,' &%9%&' ": ' L%&&' ":' R34' A-%' +":$:J:%A'
:E7%473:$A$3#'%4434'ZO66m_
/[\0
.'A-E:'&%"8$#;'A3'"'R$#"&'9"&E%'3R'[^)c'
WF(=3&'Z"'RE&&'",,3E#A'$:';$9%#'$#'A-%'6U_)''
@-%' $#9%:A$;"A$3#'3R'X'$:3A373&3;E%:' 37%#:'A-%'L"P' R34' "' :%=$J
%Q7%4$=%#A"&'Z6m_'8%A%4=$#"A$3#'3R'A-%'%SE$&$+4$E=':A4E,AE4%)'@-$:'
L":' 3+A"$#%8' +P' "' &%":AJ:SE"4%:' R$A' 3R' A-%' #
f
u:' 3R' A-%' X '
$:3A373&3;E%:' ,344%,A%8' +P' ,3=7EA%8' 9 $+ 4"A$3#"&' ,3#A4$+EA$3#:.'
%=7&3P$#;'A-%'B6<':3RAL"4%
/^f0
.'L$A-'"&&'43A"A$3#"&',3#:A"#A:'+%$#;'
%SE"&&P'L%$;-A%8)'@-%'&",W'3R'8"A"'8E%'A3'A-%'=$::$#;'$#R34="A$3#'
3#' 8%EA%4"A%8' :7%,$%:' -":' +%%#' 39%4,3=%' +P' R$Q$#;' "&&'
7"4"=%A%4:' $#93&9$#;' -P843;%#' "A3=:' A3' A-%' ,344%:73#8$#;'
,3=7EA%8' 9"&E%:)' @L3' 8$RR%4%#A' 6m' %SE$&$+4$E=':A4E,AE4%:' L%4%'
8%A%4=$#%8' +P' E:$#;' R$Q%8' ,3#:A4"$#A:' R34' A- %' -P8 43;%#J4%&"A%8'
;%3=%A4$,"&' 7"4"=%A%4:' ,"&,E&"A%8' %$A-%4' "A' A-%' O[C2lCJ
!^V="E;J,,J7N@kJ$>'Z*
%
6m
ZO[C2lC__'34'+P'=%"#:'3R'A-%'i,-%"7j'
:,-%=%'Z*
%
6m
Z,-%"7__)'O3A-',"&,E&"A$3#:'L%4%',344%,A%8' +P'E:$#;'
O[C2lCJ!^V="E;J,,J7N@kJ$>' 9$+4"A$3#"&' , 344%,A$3#:' "#8'
7439$8%8' 9%4P' :$=$&"4' :A4E,AE4"&' 7"4"=%A%4:)' U# ' 7"4"&&%&.' "'
9$+4"A$3#"&&PJ"9%4";%8':A4E,AE4%'*
f
.'L":'"&:3',3=7EA%8'+P'R$AA$#;'
A-%' % Q7%4$=%#A"&' ;43E#8J:A"A%' 43A"A$3#"&' ,3#:A"#A:' L$A-3EA' "#P'
,344%,A$3#'R34'9$+4"A$3#"&'%RR%,A:)'U#':E,-' 8 % A%4=$#"A$3#.'A-%'R$Q%8'
7"4"=%A%4:'L%4%'%9"&E"A%8' +P'=%"#:' 3R'AL3' 8$RR%4%#A':A4"A%;$%:)'
@-%'R$4:A'3#%',3#:$:A:'$#'8$4%,A&P'E:$#;'A-%',3=7EA%8' 9$+4"A$3#"&&PJ
"9%4";%8'O[C2lCJ!^V="E;J,,J7N@kJ$>'9"&E%:'Z"A'f'D.'*
f
O[C2lC
_.'
L-$&%'A-%':%,3#8'8%A%4=$#"A$3#'%Q7&3$A:'R34'A-%='A-%'*
f
-P+
v'*
%
,-%"7
w'
Z*
f
O[C2lC
J*
%
O[C2lC
_'- P+ 4$8'" 7743",-.'L-%4%'*
%
,-%"7
'"#8'*
%
O[C2lC
'"4%'
A-%' i,-%"7j' "#8' O[C2lCJ!^V="E;J,,J7N@kJ$>' %SE$&$+4$E='
9"&E%:.'4%:7%,A$9%&P)'(':%&%,A$3#'3R':A4E,AE4"&'7"4"=%A%4:'$:';$9%#'
$#' s$;E4%' [.' A-%4%' ,3 =7"4$#;' *
%
Z,-%"7_' A3' *
%
6m
Z,-%"7_' "#8' *
f
.'
L-%4%' R34' A-%' &"AA%4' "' ;%#%4$,' *
f
' $:' 7439$8%8' +%,"E:%' A-%' AL3'
:A4"A%;$%:'=%#A$3#%8'"+39%'&%8'A3'9%4P':$=$&"4'4%:E&A:'Z:%%'6U_)''
'
Figure# 2.' @-%' !B6J6*
[
' ,3=7&%Qp' :%&%,A%8' :A4E,AE4"&' 7"4"=%A%4:' Z+3#8'
8$:A"#,%:'$#'`'"#8' "#;&%:'$#' 8%;4%%:_)'I3=7EA%8'*
%
Z,-%"7_'$#'7$#W.'*
%
6m
'Z,-%"7_'
$#'+&",W.'"#8' 9$+4"A$3#"&&PJ"9%4";%8'*
f
'$#'9$3&%A)' @-%'74$#,$7"&' $#%4A$"'"Q%:'"4%'
"&:3':-3L#)'
COMMUNICATION
3
@-%'43&%'7&"P%8'+P'8$RR%4%#A'$#A%4",A$3#:'$#'8%A%4=$#$#;'A-%'39%4"&&'
:A"+$&$AP' 3R'A-%'3+:%49%8'"88E,A'-":'+%%#'$#9%:A$;"A%8' +P'=%"#:'
3R' L%&&J%:A"+&$:-%8' =38%&:)' @-%' #"AE4%' 3 R' A-%' $#A%4J=3&%,E&"4'
$#A%4",A$3#' - ":' +%%# ' E # 4"9%&%8' E:$#;' A-%' :P==%A4P' " 8"7A%8'
7%4AE4+"A$3#'A-%34P'Z6(C@_.
/^b0
'"A'A-%'6(C@[wZII!_8BC['&%9%&'$#'
,3#TE#,A$3#'L$A-'A-%'"E;J,,J7N@k'+":$:':%A)'@-%'4%:E&A:':-3L'A-"A'
A-%'%&%,A43:A"A$,'$#A%4",A$3#'$:'+P'R"4'A-%'&"4;%:A',3#A4$+EA$3#.'L-$&%'
8$:7%4:$3#' "#8' $#8E,A$3#' "4%' ,3=7"4"+&%' $#' =";#$AE8%.' "#8'
"&A3;%A-%4'"4%'&"4;%4' A-"#'A-% '%Q,-"#;%',3#A4$+EA$3#'Z: %% '6U'R34'
8%A"$&:_.' L$A-' A-%' 39%4"&&' +$#8$#;' %#%4;P' ZJ^f)X]' WFV=3&' w' 5%43'
73$#A' ,344%,A$3#_' $#' "' ;338' ";4%%=%#A' L$A-' A-%' y,-%"7y' 9"&E%'
Z&
OZ%SE$&$+4$E=_
v' J^f)ff''WFV=3&.' &
OZ%SE$&+4$E=wkCm_'
v' J [])\c' WFV=3&.'
&
OZ%SE$&+4$E=wkCmwO66m_
v'J[^)]d'WFV=3&_)'
(' 8%A"$&%8' "#"&P:$:' 3R' A-%' %&%,A43#' ,-"4;%' 4%"44"#;%=%#A'
3,,E44$#;' E73#'+$#8$#;'3R'!B6'A3'6*
[
'-":'+%%#',"44$%8' 3EA'+P'
=%"#:' 3R' A-%' :3J,"&&%8' ?"AE4"&' *4+$A"&' R34' I-%=$,"&'
N"&%#,%VI-"4;%J!$:7&",%=%#A' Z?*INVI!_' :,-%=%)
/^[0
' U#' A-%'
?*INVI!' R4"=%L34W.' A-%' 39%4"&&' ,-"4;%' 4%"44"#;%=%#A'
!
"
9ZQ.P.5_' ' ZL-3:%' R34="&' 8%R$#$A$3#' $:' ;$9%#' $#' A-%' 6U_' ," #' +%'
8%,3=73:%8'$#A3' "'L%$;-%8':E=' 3R'"'R% L'$=734A"#A.', -%=$,"&&P'
=%"#$#;RE&' ,3=73#%#A:.' !
"
9
:
)' (' :E$A"+&%' $#A%;4"A$3#' 3R' A-%:%'
A%4=:' Z:%%' 6U' R34' 8%A"$&:_' 4% AE4#:' "' ,-"4;%JR&3L' 743R$&%' !;Z<_.'
7439$8$#;.'R34'%",-'73$#A'<'"&3#;'A-%'$#A%4",A$3#'"Q$:.'A-%'" =3E #A'
3R'%&%,A43#',-"4;%'A-"A.'E73#'+3#8'R34="A$3#.'-":'R&3L#'R43='4$;-A'
A3' &% RA'",43::'"'7&"#%'34A-3;3#"&'A3'A-%' 5J "Q$:'A-43E;-'A-"A'73$#A)'
@-%' 39%4"&&' !
"
9ZQ.P.5_'4%:E&A$#;' R43='A-%'+$#8$#;'3R' !B6' A3'6*
[
'
Z:%%'s$;E 4%'6bb)b'3R'A-%'6U_':-3L:'A-"A'A-%'=3:A'$#93&9%8'"A3=:'
$#'A-%',-"4;%'4%"4 4"#;% =%#A'"4%'A-%'6J6',3E7&%'"#8'A-%'AL3'>J*'
7"$4:'73::$+&P'%#;";%8'$#'AL3' -P843;%#'+3#8:)'s3,E:$#;'3#'A-%'
6J6',3E7&%.',-"4;%'",,E=E&"A$3#'$:'3+:%49%8'$#'A-%'4%;$3#'"=$8'
A-%' "A3=:':E;;%:A$#;'%&%,A43#' :-"4$#;'":' "' ,3=73#%#A' 7"4A' 3R'
A-%$4' $# A%4",A$3#)' (:' RE&&P' 8 % A"$&%8' $# ' A-%' 6U.' A- % ' 3 9 %4"&&' ,-"4;%'
4%"44"#;%=%#A'$:'" &=3:A' % #A$4%&P'4%,39%4%8'+P' A- %'R$4:A'"#8' =3:A'
$=734A"#A ' ,3=73#%#A' Z!
"
9
b
_.' L-$,-' ="$#&P' $# 93&9%:' A-%' , -"4;%'
R&3L'+%AL%%#'A-%'AL3':E&RE4'"A3=:'Z!B6{6*
[
.':%%'+&E%',E49%'$#'
s$;E4%'^_.'"#8'L-3:%',3#A4$+EA$3#'$:' "+3EA':$Q'A$=%:'&"4;%4'A-"#'
3A-%4:)' @-%',-"4;%JR&3L'743R$&%' !;Z<_'"&3#;'A-%'$#A%4",A$3#'"Q$:'<'
"::3,$"A%8'L$A-'A-%'39%4"&&' !
"
9ZQ.P.5_'' $: ':-3L#'":' " '+&",W'&$#%'$#'
s$;E4%'^)'OP'R$Q$#;'"'7&"E:$+&%' +3E#8"4P'+%AL%%#'A-%'R4";=%#A:'
Z:%%'A-%'8":-%8'9%4A$,"&'&$#%'$#'s$;E4%'^'"#8'6U'R34'%Q7&"#"A$3#_.'"'
#%A',-"4;%'A4"#:R%4'3R'f)b['%'R43='!B6'A3'6*
[
'$:'3+A"$#%8)'
U#' L%"W&P' + 3E#8 ' "# 8' 9"#' 8%4' a""&:' ,3=7&% Q % :.' 3#&P' :="&&'
,-"#;%:' $#' % &%,A4$,' #E,&%"4' SE" 84E73&%' , 3E7&$#;' ,3 #:A"#A:' "4%'
%Q7%,A%8' L$A-' 4%:7%,A' A3' A-%' :%7"4"A%8' R4";=%#A:)' K:$#;' A-%'
*
%
6m
Z,-%"7_
'
;%3=%A4P.'A-%'
^^
6'SE"84E73&%',3E7&$#;'A%#:34'3R'%",-'
$#8$9$8E"&'=3&%,E &%'$:'43A" A%8 '$#A3'A- % '"Q$:':P:A%='3R'A-%',3=7&%Q)'
@-%'%Q7%4$=%#A"&'9"&E%'3R'A-%',3=73#%#A'"&3#;'A-%'6J6'"Q$:.'χ
//
.'
$:'bd)eez'=34% '#%; "A$9%'$#'A-%'6*
[
gggZI>
^
_
[
^^
6',3=7&%Q'A-"#'$#'
A-%'ZI>
^
_
[
^^
6
/^^0
'=3#3=%4.'L-$&%'A- % '
^^
6*
[
gggZI>
^
_
[
6',3=73#%#A'
$:'d)b^z'=34%'73 : $A$9%'A-"#'A-"A'$#'A-%'
^^
6*
[
'=3#3=%4)
/^]0
'@-$:'
3+:%49"A$3#'$:'"'RE4A-%4':A43#;'%9$8%#,%'$#':E7734A'3R'A-%'74%8$,A%8'
#3#J#%;&$;$+&%' ,-"4;%' A4"#:R%4' R43=' !B6' A3' 6 *
[
)' (#3A-%4'
:7%,A43:,37$,'%9$8%#,%'3R'A-%':A43#;'$#A%4",A$3#'+%AL%%#'A-%'AL3'
:E&RE4'"A3=:',"#'+%'R3E#8'$#'A-%',-"#;%'3R'A-%'=%": E 4%8'$#A%4#"&'
43A"A$3#'73A%#A$"&'=
>
)''U#'R4%%'!B6.'A-%'=
>
'+"44$%4'L":'R3E#8'A3'+%'
X^c)Xe]Z]]_',=
Jb
)
/^c0
'*#&P'"':="&&'+"44$%4',-"#;%'$:'3+:%49%8'$ #'
A-%' (4' ,3=7&%Q' L$A-' !B6
/^d0
.' X ^ d )b X Z^ [_' ,=
Jb
.' : E;;%:A$#;' "'
4%&"A$9%&P':="&&'$#A%4",A$3#'+%AL%%#'A-%'4"4%';":'"A3='"#8':E&RE4)'
U#' A- % ',3=7&%Q' L$A-'," 4+3#'=3#3Q$8%.
/^X0
'A-%' +"44$%4'$# ,4%":%:'A3'
X]c)c'Z^f_',=
Jb
.'L-%4%":'"':$;#$R$,"#A'8%,4%":%'ZA3'dc d)bZb]_', =
J
b
_''$:'#3 A%8'$#'A- % ',3=7&%Q'L$A-'6*
[
)'6$#,%'"#'$#A%4",A$3#'+ % AL%%#'
A-%'3QP;%#'"A3=:'3R'6*
[
'"#8'A-%'=%A-P&' A37:' L3E&8' &$W%&P'4"$:%'
A-%'+" 44$%4.'A-%'3+:%49%8'8%,4%":%'-":'A3',3=%'R43='"#'%&%,A43#'
8%#:$AP'8%7&%A$3#'3#'A-%':E&RE4'3R'!B6.'A- $: ',3#:$8%4"A$3#'+%$#;'
";"$#'$#'";4%%=%#A'L$A-'"',-"4;%'A4"#:R%4'R43='A-%'!B6'A3'A-%'
6*
[
':E&RE4)'
('?"AE4"&'O3#8'*4+$A"&'Z?O*_'"#"&P:$:
/^e0
'Z:%%'6U'R34' RE&&'8% A"$&:_.'
:-3L:'A-"A'"A'A-%'[#8'348%4'3R'7%4AE4+"A$3#'A-%'&"4;%:A',3#A4$+EA$3#'
A3' A-%' :A"+$&$5"A$3#' 3R' A-%' ,3=7&% Q' $:' 8E%' A3' A- %' $#A%4",A$3#'
+%AL%%#' A-%'6'&3#%'7"$4'3R'!B6 ' "#8' A-%' 6J*'"#A$+3#8$#;'34+$A"&'
3R' 6*
[
)''sE4A-%4=34%.' ?O*' ,-"4;%:' 73$#A' 3EA' "' &"4;%' ,-"4;%'
A4"#:R%4' R&3 L$#;'R43=' :E&RE4'$#'!B6.'A-43E;-':E&RE4'$#' 6*
[
.'A3'A-%'
3QP;%#'"A3=:.'L-$,-'$#,4%":%'A-%$4'#%;"A$9%',-"4;%:'Z:%%'@"+&%'
6b^)[_)' @- %:%' 4%:E&A:' " 4%' $#' RE &&' ";4%%=%#A' L$A-' A-%' 3A-%4'
"#"&P:%:.'A-E:' 7439$8$#;' "' RE4A-%4' ,3#R$4="A$3#' 3R' A-%' 74%9$3E:'
3+:%49"A$3#:)'
@-%'*Z6J6_'+3#8'&%#;A-'"&:3'7439$8%:'$#:$;-A:'3#'A-%'$#A%4",A$3#'
+%AL%%#'A-%':E&RE4'"A3=:)'s43='A-%'*
%
6m
Z,-%"7_':A4E,AE4%.'A-%'*Z6J
6_'3R'[)\]XZ^_'`'R3E#8'$#'A-%',3=7&%Q'$:'f)d^' `' :-34A%4'A-"#'A-%'
:E=' 3R'A-%' 9"#'8%4'a""&:'4"8$$)
/^\0
'@-$:'8$RR%4%#,%'$:':$;#$R$,"#A&P'
&"4;% 4'A-"#'A-" A'3 + :%49%8'R34'A-%' ZI>
^
_
[
*ggg6*
[
/]f0
',3=7&%Q.'R34'
L-$,-'A-%'=%":E4%8'*Z6J*_'3R'[)ee]Z[_'`'$:'f)]]'`':-34A%4'A-"#'
A-%'98a'4"8$$)'''
'
Figure#3.#I-"4;%JR&3L'743R$&%'!SZ5_'"&3#;'A-%'$#A%4",A$3#'<'"Q$:'"::3,$"A%8'L$A-'
8%#:$AP'8$RR%4%#,%:'!
"
9'"#8'!
"
9
W
'ZW'v'b.'[.'^.']_'8E%'A3'A-%'$#A%4",A$3#'+%AL%%#'
!B6'"#8'6*
[
)''
('7:%E83'8$"A3=$,'"7743Q$="A$3#'$:'3RA%#'%=7&3P%8'A3 '%:A$="A%'
A-%' : A"+$&$5"A$3#' %#%4;P'3R'AP7$,"&' 9"#' 8%4' a""&:',3=7&%Q%:)
/]b0
'
@-%' =38%&' 4%SE$4%:'A-"A' A-%' :A4"$;-AJ&$#%' T3$#$#;' A-%' ,%#A%4:J3RJ
="::'3R'A-%'AL3'7"4A#%4:'$#'A-%',3=7&%Q'$:'#%"4&P'7"4"&&%&' A3'A-%'
/J"Q$:.' ":' $:' ",AE"&&P' A-%' ,":%' R34' A-%' !B6J6*
[
' "88E,A)' @-%'
"7743",-' $:' +":%8' 3#' A-%' %:A$="A$3#' 3R' A-%' R3&&3L$#;' R34,%'
,3#:A"#Ap'
)
*
+
,-.
/
0
1
2
34
1
5
67
/
869
/
8:7
1
9
1
;
<=
>
'''' ' Zb_'
L-%4%'µ'$:'A-%'4%8E,%8'="::.'?
2,
'$:'A-%',%#A%4' 3 R'=": : '8$:A"#,%'
+%AL%%#'A-%'AL3'=3#3=%4:.'#'"#8'8'"4%'A-%'43A"A$3#"&',3#:A"#A:.'
"#8'@
6'
$:'"',%#A4$RE;"&'8$: A34A$3#' , 3 # :A"#A)'>%4%.'A-%'?
2,
'9"&E%'$:'
A"W%# 'R43='A-%
'
*
)
%&
Z,-%"7_
1
:A4E,AE4%)'@-%'7:%E83'8$"A3=$,'=38%&'
A-%#'%=7&3P:'"'2%3#"48JF3#%:'73A%#A$"&'A3'8%A%4=$#%'A-%'+$#8$#;'
%#%4;P'3R'A-%',3=7&%Q.'&
#
p'
?
7
+
,
@:
)
*
A
BC
:
' ' ' ' ' ' ' Z[_'
@-$:' ;$9%:' "' 4%:E&A' 3R' &
#1
v' J]^)dZd_' WFV=3&.' L-$,-' :$;#$R$,"#A&P'
8$RR%4:' R43=' A-%' 9"&E%' 74%8$,A%8' +P' A-%' i,-%"7j' :,-%=%' Z:%%'
"+39%_' 3R' J[^)c' WFV=3&)' (:' A-%' ",,E4",P' 3R' A-%' :7%,A43:,37$,'
,3#:A"#A:'"#8'A-%'*
)
%&
':A4E,AE4%'3+A"$#%8'+P'A-%'i,-%"7j'=38%&'
COMMUNICATION
4
"4%'&"4;%&P'83,E=%#A%8.'L%'=E:A',3#,&E8%'A-"A'"':$=7&%'2%3#"48J
F3#%:'73A%#A$"&'$:'#3A'"+&%'A3'8%:,4$+%'A-%'+$#8$#;'3R'!B6'"#8 '
6*
[
.'A- % '4%" :3 # '&$W%&P'+%$#;' 4% &"A%8'A3'A-%'74%:%#,%'3R'3A-%4'&3 L'
R4%SE%#,P'=38%:.'":'RE&&P'8$:,E::%8'$#'A-%'6U)'
U#':E=="4P.'$#'A- % ';":'7-":%',3=7&%Q'+%AL%%#'!B6'"#8'6*
[
'"'
:E&RE4J:E&RE4' #3#,39"&%#A' $#A%4",A$3#' -":' +%%#' E#9%$&%8.' L-$,-'
&"4;% &P'74%9"$&:'39%4'A-%'IJ>ggg*'-P843;%#'+3#8:)'O3A-'A-%'?O*'
"#8' ?*INVI!' "7743",-%:'73$#A'3EA' "'="4W%8',-"4;%'A4"#:R%4'
$#93&9$#;'A-%': E &R E4' " A 3 =:.'"&:3' , 3 #R$4=%8'+P'A-%'
^^
6'SE"84E73&%'
,3E7&$#;',3#:A"#A'"#"&P:$:)'@-%'%&%,A43:A"A$,',3#A4$+EA$3#'A3'A-%'6J
6' $#A%4",A$3#' 7&"P:' "'83=$#"#A' 43&%' $#' :A"+$&$5$#;' A-%' =3&%,E&"4'
"88E,A' ",,348$#;' A3' "' 6(C@' "#"&P:$:)' @-%' ,3=7EA%8' +$#8$#;'
%#%4;P' 9"&E%' 73$#A:' 3EA' A-"A' A-%' :A4%#;A-' 3R' A-%' :E&RE4J:E&RE4'
$#A%4",A$3#'$:':$=$&"4'A3'A-" A'AP7$,"&'$#'#%EA4"&'-P843;%#'+3#8:)'('
#3A' &%::' $=734A"#A' 4%:E&A' 3R' A-%' 74%:%#A' :AE8P' $:' A-%' ",,E4"A%'
:A4E,AE 4"&',-"4",A%4$5"A$3#'3R'A-%'!B6J6*
[
',3=7&%Q)'@-$:'4%&$%:'
3#'A-%':%=$J%Q7%4$=%#A"&'%SE$&$+4$E=':A4E,AE4%'"7743",-.'"77&$%8'
R34' A-%' R$4:A' A$=%' A3' "' =3&%,E&"4' ,3=7&%Q.' L-$,-' ,3=+$#%:'
,3=7EA%8' 9$+4"A$3#"&' ,344%,A$3#:' L$A-' A-%' %Q7%4$=%#A"&&P'
8%A%4=$#%8' 43A"A$3#"&' ,3#:A"#A:' 3R' :%9%#' $:3A373&3;E%:)' UA' $:'
#3A%L34A-P' A-"A' A-%' :%=$J%Q7%4$=%#A"&' %SE$&$+4$E=' :A4E,AE4%' $:'
9%4P' ,&3:%' A3' $A:' 7E4%&P' A-%34%A$,"&' ,3E#A%47"4A' +":%8' 3 #' A-%'
i,-%"7j',3=73:$A%'"7743",-)''
'
Experimental#Section#
@-%',3=7&%Q'$:'R34=%8'$#'"'43A"A$3#"&&P',3&8'Z&%::'A-"#']'D_.':E7%4:3#$,'T%A'
A-"A'$:'%Q7"#8%8'R43='"'=$QAE4%'3R'b)]J[)fz'8$=%A-P&':E&R$8%.'b)fJb)^z'6*
[
'
$#' (4' Z\\)\\\z' 7E4$AP_' "A' :A";#"A$3#' 74%::E4%' 3R' b' +"4)' U#$A$"&'
=%":E4%=%#A:' L%4%' ="8%' E:$#;' A-%' +43"8+"#8' U BC (I@ ''
ZU#J7-":%VSE"84"AE4%J7-":%JB38E&"A$3#' C"::";%J(,SE$4%8JI3-% 4%#,%'
A%,-#$SE%_' :7%,A43=%A%4
/][0
' +%AL%%#' XJbd' H>5)' sE4A-%4' =%":E4%=%#A:'
L%4%' ="8%' E:$#;' A-%' I*O<(' ZI3"Q$"&&P' (&$;#%8' O%"=' <%:3#"A34'
(44"#;%=%#A_' s3E4$%4' @4"#:R34=' B$,43L"9%' :7%,A43=%A%4
/]^0
.' L-$,-'
743&3#;:'A-%'3+:%49"A$3#'A$=%',3=7"4%8'A3'"'s"+4PJC%43A'AP7%',"9$AP':%AE7'
E:%8' $#' A-%' :AP &%' 3R' O"&&%' "#8' s&P;"4%
/]]0
' A3' 4%,348' =3&%,E&"4' :$;#"&:.'
74$="4$&P'43A"A$3#"&'A4"#:$A$3#:)'
Acknowledgements##
@-%' "EA-34:' ",W#3L&%8;%' A-%' (&%Q"#8%4' 93#' >E=+3&8A'
s3E#8"A$3#.'A-%'2"#8'?$%8%4:",-:%#.' "#8'A-%' !sH'R34'R$#"#,$"&'
:E7734A.'"#8'a)'O)'H"48%#'R34'-%&7RE&'8$:,E::$3#:"#@-$:'L34W'-":'
"&:3'+%%#':E7734A%8'+P'BUK<'iC<U?'[fbcj'RE#8:'ZH4"#A'?E=+%4'
[fbcsc\F^<_.'+P'A-%'K#$9%4:$AP'3R'O3&3;#"'Z<s*'RE#8:_.'"#8'+P'
6,E3&"' ?34="&%' 6E7%4$34%' ZH4"#A' ?E=+%4'
6?6be|O|@(6U?(@*_)' @-%' 6B(<@q6?6' 2"+ 3 4"A34P'
Z-AA7pVV:="4A):#:)$A_' $:' ",W#3L&%8;%8' R34' 743 9$8$#;' -$;-J
7%4R34="#,%',3=7EA%4'R",$&$A$%:)'@-%'"EA-34:' "&:3'",W#3L&%8;%'
B4)'(&%::$3'B%&&$'R34'A-%';4"7-$,"& '"+:A4",A'74%7"4"A$3#)'
Keywords:' :%=$J%Q7%4$=%#A"&' %SE$&$+4$E=' :A4E,AE4%' }' 43A"A$3#"&'
:7%,A43:,37P'}'SE"#AE=',-%=$:A4P'}'+3#8' "#"&P:$:'}'%#%4;P'"#8'
,-"4;%'8%,3=73:$A$3#'=38%&:'
#$%&# '"# ("# ')*+,#-"./"# 0)1*2,# 3"# 4"# '5678)62)6,# 9"# 4"# :)**;*27+*,# <"#="# 3)5*>)??,# J.%
Med.%Chem"#2015,#58,#@ABAC@@AB"#
$D&# ("#E"#F;GH,#I"#3"#-6+*)6,#'"#<)J5?,#("#352*5*;,#/"#K+6+>;7L,#("#9"#K+17L,#/"#/GM);*)6,#
("N"#O6;)P)?,#ACS%Chem.%Biol"#2016,#11,#Q@BRQS@"#
$A&# :"# OM5J?T5?,# # ="# I5*21?T,# '"# 9"# I+?U)*,# /"# K5VV)W./GM;XX)6,# :"# N"# ')P;?5GY15,#
Biochemistry##2013,#SD,#Z@[[RZS%@"#
$@&# '"#="#I6)2)6W)*,#\"#9+J)L,#4"#3"#0+6H,#J.%Am.%Chem.%Soc"#2003,#125,#Q%QB.Q%Q["##
$S&# ]"#:)*+GGM;+,#3"#3)*U+?;GGM;+,#<"#O5W;*57+,#^"#'56+*),#Can.%J.%Chem"#2016,##94,#
%_ZSR%_QZ"#
$Z&# 3".-"#K5*,#0"./"#E;*,#'"#-T1#01,#`"#NM+;,#O"./"#0+18,#/".E"#-;V,#J.%Mater.%Chem.%A##
2016,##4,#%ABS[R%ABZS"#
$Q&# N"#F5?5*7;*,#="#3+*G+V8?),#="#9)#:)6 W+*,#E".:"# N+6*56U,#Spectrochim.%Acta%A#
2017,#187,#@[RZ_#5*U#6)X)6)*G)W#7M)6);*"#
$B&# /"#')*L,# E"# 9aJ)L.=*U56;5W,#E"#356)U5,#<"#/5H5;,# /"#357;?),#Angew.%Chem.%Int.% Ed.%
2017,#56,#B%D#RB%S"#
#$[&# 5b#9"#NM)*,##E"#\;5*2,#0"#cM5+,#d"#05*,#J.%Am.%Chem.%Soc"#2018,#140,# Q_Q[CQ_BDe#8b#
("#I?);7)6,#I"#K58)6M51)6,#4"#'"#`)6L,#F"#(+V;*2)6,#N"#'?);M+?U)6,#Chem.%Rev.%2018,#
118,#D_%_.D_@%"#
$%_&# E"#F5*X6?fH,#=U5V#:ghU5,#c"#:5Ui?H+Ph#="#:)G;*5,#E"#35GMhj)H,#3"#9)JkfH,#E"#K+?18,#
=?)k#(lm;jH5,#4"#K*TH,#:"#K+8L5,#Angew.%Chem.%Int.%Ed.#2014,#53,#%_%A[#R%_%@D"#
$%%&# 5b# 4"# E"# :5WG+),# -"# '"# 9;*2,# /"# 9"# N+GH6+X7,# J.% Am.% Chem.% Soc"# 2017,# 139,#
%S%Z_C%S%ZQe#8b#n"# =UM;H56;,#/"# /GM);*)6,#Chem.%Phys.%Lett"#2012,#532,#A%RASe#Gb#
`"#`5*2,# '"#E;,#0"# c M5*2,# J.%Phys.%Chem.%A#2009,#113,#B%ADRB%ASe#Ub#3"#K"#-+?hg,#
:"# K+8L5,# Chem.% Rev"# 2016,# 116,# S%SSCS%BQe# )b# ="# '51Lh,# O"# E"# 3++; 86+)H,#= "#
F6+*7)65,##ChemPhysChem##2015,#16,#D@[Z#RDS%Q"#
$%D&# I"# ("# 4)W;65o1,# :"# /"# K+,# 9"# -?++,# ="# N"# 9)2+*,# ("# 356Y156U7,# :"# 3)765*2+?+,# :"#
:+?;7L)6,#I"#()W*57;,#-"#(;WW5*)*,#Pure%Appl .%Chem.%2013,#85,#%Q%%R%Q%A"#
$%A&# :"#:+?;7L)6,##E"#/"#31665T,#J.%Comput.%Chem"#2018,#39,#@Z@R@Q%"#
$%@&# 0"#I)8+)W,#]"#4)#^+W,#`"#="#K)66)8+17,#New%J.%Chem"#2018,#42,#%_SZA.%_SQ%"#
$%S&# ="#N"#9)2+*,#Phys.%Chem.%Chem.%Phys.,#2017,%19,#%@BB@..%@B[Z"#
$%Z&# N"#:1LL56;*;,#^"#'56+*),#Phys.%Chem.%Chem.%Phys"#2011,#13,#Q%SB.Q%ZZ"#
$%Q&# 5b# I"4"# :16P;W# ppp,# ("E"# '567?)77,# J.% Chem.% Phys"# 1982,# 76,# %[%_.%[%Be# 8b# -"#
(52M5P5GM56;,# I"`"#O61GHW,#E"="# :+J?),#3"#K)5U.I+6U+*,#Chem.%Phys.%Lett"#1989,#
157,#@Q[.@BA"#
$%B&# 5b# O"K"# 41**;*2# E6",# J.% Chem.% Phys.# 1989,# 90,# %__Q.%_DA"# 8b# 4"]"# `++*,# O"K"#
41**;*2#E6,#J.%Chem.%Phys"#1993,#98,#%ASB"##
$%[&# N"#3q??)6,#3"/"#:?)WW)7,#Phys.%Rev.#1934,#46,#Z%B.ZDD"#
$D_&# 4"# :5J+1k)H,# 3"# ("# =?;)P,# Molecular% Vibrational−Rotational% Spectra,# ]?W)P;)6,#
=VW7)6U5V,#1982"#
$D%&# 5b# /"# I6;VV),% J.% Chem.% Phys"# 2006,# 124,# _A@%_Be# 8b# /"# I6;VV),# E"# =*7+*T,#/"#
]M6?;GM,#K"#-6;)2,#J.%Chem.%Phys"#2010,#132,#%S@%_@" #
$DD&# 5b#]"#:5J5o5H,# K"#( "# 9)P)6)*7L,#E"#cM)*2,#4"# I"#O61M?56,# J.%Chem.% Theory% Comput.#
2009,#5,#%%[Q.%D_D"#8b#O"#F+6*56+,#3"#';GLTWH+,#E"#'?+;*+,#^"#'56+*),#Phys.%Chem.%
Chem.%Phys"#2016,#18,#B@Q[.B@[_"#
$DA&# E"#-"#I"#`57W+*#;*#Vibrational%Spectra%and%Structure,#^+?"#Z,#]U"#E"("#416;2,#]?P;W;)6,#
<)>#0+6H,#=VW7)6U5V#1977"#
$D@&# #p"#3"#3;??W#;*#A30)2B0/*%Spectroscopy:%Modern%Research,#]UW"#-"#<"#(5+#5*U#N"`"#
357M)>W,#=G5U)V;G#:6)WW,#<)>#0+6H#1972"#
$DS&# K"#K567>;2,#K"#46);L?)6,#Z.%Naturforsch##1996,#51a,#[DA.[AD"#
$DZ&# ^"# ^5*,# `"# /75M?,# K"# ^"# 9"# <21T)*,# Phys.% Chem.% Chem.% Phys.% 2015,# 17,#AD%%%r
AD%%@"#
$DQ&# 4"#F)??)6,#J.%Chem.%Phys"#1993,#98,#Q_S[.Q_Q%"#
$DB&# O"#K)?25H)6,#`"#-?+JJ)6,#K"#-+GM,#E"#<+25,#J.%Chem.%Ph y s"#1997,#106,#[ZA[.[Z@Z"#
$D[&# /"#F"#'+TW,#F"#')6*56U;,#Mol.%Phys.#1970,#19,#SSA.SZZ"##
$A_&##3"#3)*U+?;GGM;+,# ]"#:)*+GGM;+,#4"#9;G56;,#<"#O5W;*57+,#^"#'56+*),#J.%Chem.%Theory%
Comput.#2017,#13,#A_Z_.A_QS"#
$A%&# '"#E)L;+6WH;,#("#3+WLT*WH;,#-"#/L5? )>;GL,#Chem.%Rev.#1994,#94,#%BBQ#R#%[A_"##
$AD&# 5b# I"# ';W7+*;,# /"# (5VJ;*+,# F"# O565*7)??;,# 9"# ')?J5WW;,# J.% Chem.% Phys.# 2015,# 142,#
_B@%%D"#8b#="#/5?P5U+6;,#3"#F1Ws,#I"#35*G;*;,#/"#(5VJ;*+,#^"#'56+*),#J.%Comput.%
Chem.# 2018,# M77JWtuuU+;"+62u%_"%__DuoGG"DSSDA# Gb# 3"# F1Ws,# p"# (;V+?U;,# I"#
F5GGM)77;,#/"#(5VJ;*+,#^"#'56+*),#Chem.%Comm"#2018,% 54,#DA[Q.D@__"##
$AA&# n"#-6)7WGMV)6 ,#K"#K567>;2,#K"#46);L?)6,#J.%Mol.%Spectrosc.#1995,#174,#%AQ.%S_"#
$A@&# K"#/"#:"#3v??)6,#E"#F56M++V5*U,#]"#="#N+M)*,#'"#'61J85GM)6.I57)M+1W),#3"#/GMwX)6,#
="##'51U)6,#I"#`; **)>;WW)6,#J.%Mol.%Spectrosc"#2000,#201,#%.B"#
$AS&# ="#E586;,#^"#^5*,#K"#^"#9"#<21T)*,#K"#3+1M;8,#F"#->58;5# OGM5*5,##9"#35*G)6+*,#`"#
/75M?,#p"#-?);*)6,#A&A#2016,#589,#=%DQ" #
$AZ&# 0"# O575V;75*;,# ="# /57+,# 0"# -5>5WM;V5,# <"# xM5WM;,# E"# 3"# 9+'1),#]"# K;6+75,# J.%Mol.%
Spectrosc"#2009,#257,#%%.%["#
$AQ&# ="#/57+,#0"#-5>5WM;V5,#]"# K;6+75,#J.%Mol.%Spectrosc"#2010,#263,#%ASR%@%"#
$AB&# ]"#4"#I?)*U)*;*2,#N"#("#95*U;W,#F"#`);*M+?U,#WIREs%Comput.% Mol.%Sci.%2012,# 2,#%.
@D"#
$A[&# 3"#35*7;*5,#="#N"#NM5V8)6?;*,#("#^5?)6+,#N"#E"#N65V)6,#4"#I"#O61M?56,#J.%Phys.%Chem.%
A#2009,#113,#SB_Z.SB%D"#
$@_&# E"#E"#xM,#-"#`"#K;??;2#pp,#("#9"#-1GLH+>WH;,%Inorg.%Chem.#1991,#30,#@SBA.@SBB"#
$@%&# 5b# 4"#E"#3;??)*,#Can.%J.%Chem"#1985,#63,#%@QQ.%@Q[e#8b#/"#]"#<+P;GH,#/"#E"#K566;W,#-"#N"#
E5*U5,#`"#-?)VJ)6)6,#Can.%J.%Phys"#1975,#53,#D__Q.D_%S"#
$@D&# 3"# -"#E5M*,#4"#="# 4)>5?U,#4"#`5GMWV17M,#E".n"#I658+>,# /"#N"#3)M6+765,#J.% Mol.%
Spectrosc.%2012,#280,#S@.Z_"##
$@A&# E"#n"#I658+>,#`"#/75M?,#K"#46);L?)6,#Rev.%Sci.%Instrum.#1996,#67,#@_QD.@_B@"#
$@@&# O"#E"#'5??),#`"#K"#F?T256),#Rev.%Sci.%Instrum"#1981,#52,#AA.@S"